Recently, lithium secondary batteries have been used in various fields including portable electronic devices, such as mobile phones, personal digital assistants (PDAs), and laptop computers. In particular, in line with growing concerns about environmental issues, research into lithium secondary batteries having high energy density and discharge voltage as a power source of an electric vehicle, which may replace vehicles using fossil fuels such as gasoline vehicle and diesel vehicle, one of major causes of air pollution, has been actively conducted and some of the research are in a commercialization stage. Meanwhile, in order to use a lithium secondary battery as a power source of the electric vehicle, the lithium secondary battery must maintain stable power in a usable state of charge (SOC) range along with high power.
An electric vehicle is classified as a typical electric vehicle (EV), battery electric vehicle (BEV), hybrid electric vehicle (HEV), or plug-in hybrid electric vehicle (PHEV) according to a power source thereof.
The HEV among the above electric vehicles, as a vehicle obtaining a driving force from the combination of typical internal combustion engine (engine) and electric battery, has a mode, in which the driving force is mainly obtained through the engine while the battery assists insufficient power of the engine only in the case of requiring more power than that of a typical case, such as uphill driving, and the SOC is recovered again through charging the battery during the stop of the vehicle. That is, the engine is a primary power source in the HEV, and the battery is an auxiliary power source and is only used intermittently.
The PHEV, as a vehicle obtaining a driving force from the combination of engine and battery rechargeable by being connected to an external power supply, is broadly classified as a parallel-type PHEV and a series-type PHEV.
In the parallel-type PHEV, the engine and the battery are in an equivalent relationship to each other as a power source and the engine or the battery may alternatingly act as a primary power source according to the situation. That is, the parallel-type PHEV is operated in a mutually parallel mode, in which the battery makes up for insufficient power of the engine when the engine becomes a primary power source and the engine makes up for insufficient power of the battery when the battery becomes a primary power source.
However, the series-type PHEV is a vehicle basically driven only by a battery, in which an engine only acts to charge the battery. Therefore, since the series-type PHEV, differing from the HEV or the parallel-type PHEV, entirely depends on the battery rather than the engine in terms of driving of the vehicle, maintaining of stable output power according to battery characteristics in a usable SOC range becomes a very important factor for driving safety in comparison to other types of electric vehicles. The EV also requires a battery having a wide available SOC range.
Meanwhile, with respect to LiCoO2, as a typical cathode material of a high-capacity lithium secondary battery, practical limits of an increase in energy density and power characteristics have been reached. In particular, when LiCoO2 is used in high energy density applications, oxygen in a structure of LiCoO2 is discharged along with structural degeneration in a high-temperature charged state due to its structural instability to generate an exothermic reaction with an electrolyte in a battery, and thus, it becomes a main cause of battery explosion. In order to improve the safety limitation of LiCoO2, the use of lithium-containing manganese oxides, such as LiMnO2 having a layered crystal structure and LiMn2O4 having a spinel crystal structure, and lithium-containing nickel oxide (LiNiO2) have been considered, and a great deal of research into layer-structured lithium manganese oxides, in which Mn as an essential transition metal is added in an amount larger than those of other transition metals (excluding lithium) to layer-structured lithium manganese oxide as a high-capacity material, has also been conducted.
In particular, attention has been drawn recently to whether composite dimensional manganese oxide (CDMO) of the following chemical formula, in which Li2MnO3 and (γ/β)-MnO2 are combined by substituting a part of MnO2 with lithium (Li), can be used as a cathode active material.xMnO2.(1−x)Li2MnO3(0<x<1)
As described above, the CDMO has a composite structure in which Li2MnO3 and (γ/β)-MnO2 are combined by substituting a part of MnO2 with Li. Since the crystal structure only including pure (γ/β)-MnO2 may easily collapse as charge and discharge proceed, lifetime characteristics of the secondary battery may be poor when the CDMO is used as a cathode active material. However, since Li2MnO3 and (γ/β)-MnO2 form a composite structure, the CDMO may have a relatively solid structure. Thus, research into using the CDMO as a cathode active material having high capacity and improved lifetime characteristics by increasing structural stability has been continuously conducted.
However, since charge and discharge may not be possible by using the CDMO alone, the use of the CDMO as an active material of the lithium secondary battery may not be possible. Therefore, the CDMO may not be used as a cathode active material yet.